Carbohydrate chemistry II

Structure and Isomerism

Dr. Vijay Marakala, MD.

Assistant professor
BIOCHEMISTRY
SIMS & RC
Structure of
monosaccharide

Fisher Haworth X-ray

projection projection diffraction
The straight Cyclic analysis
chain formula or Boat and
structural ring chair form
formula structure
 Straight chain

Ring structure

Chair form
Isomerism
The compounds possessing identical
molecular formula but different
structures are called isomers.
Various types of isomerism
1. Structural isomerism
2. Stereoisomerism
Structural isomerism
Same molecular formulae but differ
from each other by having different
structures.
Stereoisomerism
Same molecular formula and same
structure but they differ in
configuration.

That is arrangement of their atoms in

space.

Presence of asymmetric carbon

atoms allow the formation of
stereoisomerism
Stereoisomerism
The important types of
stereoisomerism associated with
glucose are
D and L isomerism
Optical isomerism
Epimerism
and anomerism
D and L
isomerism
Optical isomerism
Optical activity is the capacity of a
substance to rotate the plane
polarized light passing through it.

Clockwise direction
Dextrorotatory(d) or (+)

Counterclockwise direction
Levorotatory(l)or (-)
Optical isomerism

Chiral compounds rotate polarized light clockwise

or counter clockwise through certain angle
Epimerism

Epimerism is the stereoisomerism if

two monosaccharides differ from
each other in their configuration
around a single specific carbon(other
than anomeric) atom.
Epimerism
Anomerism
These are isomers obtained from the
change of position of hydroxyl group
attached to the anomeric carbon e.g.
and glucose are 2 anomers.
Also and fructose are 2 anomers.
Anomerism
Mutarotaion
Mutarotaion is defined as the change
in the specific optical rotation by the
interconversion of and forms of D
glucose to an equilibrium mixture
Structure of
oligosaccharides
Disaccharides
Disaccharide
s

Nonreduci
Reducing ng

Maltose
Lactose Sucrose
Isomaltose
 DISACCHARIDES
These are glycosides formed by the
condensation of 2 simple sugars.

If the glycosidic linkage involves the carbonyl

groups of both sugars (as in sucrose) the
resulting disaccharide is non-reducing.

On the other hand, if the glycosidic linkage

involves the carbonyl group of only one of
the 2 sugars (as in maltose and lactose) the
resulting disaccharide is reducing.
 POLYSACCHARIDES

These are formed by the condensation of n molecules of

monosaccharides with the removal of n -1 molecules of
water. Since condensation involves the carbonyl groups of
the sugars, leaving only one free carbonyl group at the
end of a big molecule, polysaccharides are non-reducing.

They are of 2 types:

1. Homopolysaccharides (e.g. Starch, Glycogen, cellulose).

2. Heteropolysaccharides (e.g. glycosaminoglycans,

glycoproteins)
 -1,6 linkage
between two
glucose units

- 1,4 linkage between

two glucose units
he ability to digest cellulose
s found only in microorganisms
hat contain the enzyme
Cellulase.
ertain animal species (e.g. Cow)
tilize such organisms in their
igestive tracts to digest cellulose
 Monosaccharides
Can be classified as

Aldoses Ketoses Isomers Epimers Enantiomers

if they containif they containif they contain if they if they are
Aldehyde Keto Same Differ in Mirror images
group group chemica configuration of each other
H-C=O C=O l around one
formula specific
carbon atom
can link to form

Disaccharides Oligosaccharides Polysaccharides

e.g., can be
sucrose = glucose +
fructose
Lactose = galactose +
Homo- Hetero-
glucose
Maltose = glucose + e.g., e.g.,
glucose Starch, glycogen, GAGs
cellulose